JP4819484B2 - Toner manufacturing method - Google Patents

Description

  The present specification relates to a toner, a method of using the toner, and a method of manufacturing the toner.

  Patent Document 1 shows a method for producing colored polymeric particles in which two or more different dyes are covalently bonded to polymeric particles after particle synthesis.

  U.S. Patent No. 6,057,049 shows a dry toner produced by suspension polymerization of a styrene-acrylic acid monomer mixture in the presence of a polyester-promoted colloidal silica suspending agent that does not contain other hydrophilic polymers.

  Patent Document 3 shows a toner resin produced by emulsion polymerization using an alicyclic diacid emulsifier.

  Patent Document 4 discloses a step of producing a colored polymer particle as a core component by suspension polymerization of a monomer composition in an aqueous dispersion medium, a step of adding at least one monomer for a shell component, The toner manufacturing method containing this is shown.

  Patent Document 5 shows a polymerized toner including polymer particles obtained by polymerizing a monomer for a shell, wherein the monomer for shell has a glass transition temperature higher than that of a polymer that forms core particles.

  Patent Document 6 shows a polymer production method including a step of producing a polymer by emulsion polymerization of a vinyl aromatic monomer, a conjugated diene monomer, and an acrylate monomer in the presence of an alicyclic diacid emulsifier. Yes.

  Patent Document 7 shows a method for producing a polymeric particle material using a monomer capable of free radical polymerization, a free radical initiator, and a stable free radical compound. This production method prepares a prepolymer mixture, controls the initiation, and limits the polymerization of the monomer to a first bulk polymerization step, followed by almost complete polymerization of the monomer. And a second stage microemulsion polymerization process.

US Pat. No. 4,880,432 US Pat. No. 4,912,009 US Pat. No. 5,852,151 US Pat. No. 5,952,144 US Pat. No. 6,136,490 US Pat. No. 6,136,492 US Pat. No. 6,469,094

  Polymers used for known resin applications generally include acrylic acid-containing monomers. These polymers are then agglomerated by, for example, polyaluminum chloride (PAC) treatment. However, acrylic acid-containing monomers are difficult to incorporate into stable free radical polymerization methods such as those combined with styrene. The present specification describes a method for producing latexes using a stable free radical polymerization method, which can then aggregate and coalesce latexes into toner particles. is there.

  Aspects of the present specification are as follows. A first heating step for heating a latomer mixture comprising at least one free radically polymerizable monomer and at least one alkylene anhydride; and a second heating step for heating the latomer mixture to produce polymeric particles. And a step of binding at least one amine to the polymeric particles, wherein the second heating step is at a higher temperature than the first heating step. Generating a resin microemulsion comprising polymeric particles comprising at least one free radically polymerizable monomer compound and at least one alkylene anhydride, the microemulsion with at least one colorant, and at least one Mixing an amine with optionally at least one wax, heating the resulting mixture at a temperature near or below the glass transition temperature (Tg) of the resin emulsion, and the resulting mixture. Heating the resin emulsion at a temperature near or above the glass transition temperature (Tg) of the resin emulsion. A first heating step for converting the latomer mixture comprising at least one free radically polymerizable monomer at a low conversion rate, then adding at least one alkylene anhydride, and converting the latomer mixture at a low conversion rate; A latex manufacturing method comprising: a second heating step; a third heating step for heating the latomer mixture to produce polymeric particles; and binding at least one amine to the polymeric particles. In addition, other aspects of the present description also relate to toner products obtained from the methods set forth herein.

  Latexes can be aggregated and combined into toner particles by a method for producing latexes using a stable free radical polymerization method.

  The methods disclosed herein produce latexes that can be aggregated and coalesced into toner particles.

  The present specification includes a first heating step of heating a latomer mixture comprising at least one free radically polymerizable monomer and at least one alkylene anhydride, and heating the latomer mixture to produce polymeric particles. Figure 2 illustrates a latex manufacturing method that includes a second heating step and a step of binding at least one amine to the polymeric particles.

The first heating step of the first mixture is performed at a heating temperature of, for example, about 50 to about 145 ° C., more specifically, for example, about 120 to about 130 ° C., for a reaction time of, for example, about 5 minutes to about 4 hours, and more For about 20 minutes to about 1 hour. The heating conditions can be changed depending on, for example, the reaction scale and the desired result.

The at least one free radical polymerizable monomer contains a functional group, and known free radical polymerizable monomers such as styrene monomers (styrene sulfonic acids, 4-vinylbenzoic acid, etc.), conjugated compounds, 9- Vinylcarbazole compound, vinyl chloride compound, vinyl acetate compound, represented by the formula (CH ₂ ═CH) COOR—COOH (wherein the R group can be a spacer aliphatic group for different hydrophilicity, for example) Acrylic acid monomers and derivatives thereof (butyl acrylate, ethyl acrylate, hydroxyethyl acrylate, etc.), formula (CH ₂ ═CCH ₃ ) COORCOOH (wherein the R group is, for example, a spacer for different hydrophilicity) Methacrylic acid esters and their derivatives (Methyl methacrylate, butyl methacrylate), unsaturated monomers etc., and are selected from the group consisting of mixtures thereof. The content of the at least one free radical polymerizable monomer in the latomer mixture is, for example, from about 85 to about 99% by weight relative to the at least one alkylene anhydride.

  At least one free radical polymerizable monomer is copolymerized with at least one alkylene anhydride. For example, at least one free radical polymerizable monomer such as styrene is copolymerized in a 1: 1 ratio with, for example, maleic anhydride (MA). In an embodiment, copolymerization results in a polymer having the formula (AB) n where A is at least one stable free radical polymerizable monomer and B is at least one alkylene anhydride. Generate. If at least one free radical polymerizable monomer present in the first mixture is greater than at least one alkylene anhydride, polymerization occurs until all of the at least one alkylene anhydride is consumed, and then at least one free radical It is thought that the remainder of the radically polymerizable monomer is polymerized. In an embodiment, the first mixture includes three types of polymers, such as poly (styrene / MA), poly (styrene / MA-b-styrene) block copolymer, polystyrene, and the like.

  The at least one alkylene anhydride may be any anhydride having a double bond as long as the anhydride is polymerizable with at least one free radical polymerizable monomer. Examples of at least one alkylene anhydride include maleic anhydride, 2,3-dialkylmaleic anhydride such as 2,3-dimethylmaleic anhydride, 2,3-diphenylmaleic anhydride, tetrahydrophthalic anhydride Products, N-methyl isatoic anhydride, and the like, and mixtures thereof, but are not limited thereto. The latomer refers to, for example, a latex mixture. In the latomer mixture, each component (for example, monomer and alkylene anhydride) is only one kind, or may be composed of two or more kinds. The content of the at least one alkylene anhydride in the latomer mixture is, for example, from about 0.1 to about 20% by weight relative to the at least one free radical polymerizable monomer.

  In embodiments, the components of the latomer mixture and the heating conditions of the latomer mixture are selected such that bulk polymerization or solution polymerization of at least one free radical polymerizable monomer and at least one alkylene anhydride occurs.

  If desired, at least one free radical initiator may be added to the latomer mixture. Free radical initiators include, for example, benzoyl peroxide, di-t-butyl peroxide, 4,4′-azobisvaleronitrile, 4,4′-azobis (cyanohexane), hydrogen peroxide, t-butyl hydroperoxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), 4,4 Selected from the group consisting of peroxides and diazo compounds such as' -azobis (4-cyanopentanoic acid), potassium persulfate, and potassium aminopersulfate. At least one free radical initiator is soluble in the immiscible liquid. The content of at least one free radical initiator is, for example, from about 0.01 to about 5%, more specifically from about 1 to about 3% by weight, based on the at least one free radical polymerizable monomer.

  The latomer mixture may be dispersed in the immiscible liquid using at least one surfactant. The immiscible liquid may be any aqueous solution or mixture such as water as long as it does not dissolve the monomer or prepolymer resin contained in the latomer mixture.

The at least one surfactant can be selected from the group consisting of anionic, cationic, amphoteric, and nonionic surfactants customarily used in emulsion polymerization. In embodiments, the at least one surfactant is an ionic surfactant, and this type of surfactant is generally suitable for the higher temperatures associated with the present method. Examples of anionic surfactants include, but are not limited to, alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and the like. For example, α-olefin (C ₁₄ -C ₁₆₎ sulfonate, sodium and the like. A typical surfactant is an alkali metal alkylaryl sulfonate. In embodiments, suitable anionic surfactants include alkyl sulfonates or arylalkyl sulfonates such as sodium dodecylbenzene sulfonate (SDBS). A list of suitable stabilizing compounds, such as surfactants, useful in the method of the present invention is given in the book “McCutcheon's Emulsifiers and Detergents 1981 Annual”.

  The at least one surfactant can be used in various amounts, for example if a good microemulsion can be achieved by exceeding the critical micelle concentration (CMC). The content of the at least one surfactant may be from about 1 to about 10% by weight, for example from about 2 to about 5% by weight, more for example from about 2 to about 3% by weight, based on the weight of the immiscible liquid. it can.

  If necessary, at least one stabilizer may be added to further reduce diffusion due to Ostwald ripening. The at least one stabilizer is a low water solubility or almost insoluble compound such as long chain hydrocarbons having from about 10 to about 40 carbon atoms, such as alcohols having from about 15 to about 25 carbon atoms. , Mercaptans, carboxylic acids, ketones, amines, hydrocarbons, or other long-chain molecules with or without stable free radicals or functional groups that do not significantly affect the chemistry of the microemulsion Such as dodecyl mercaptan, hexadecane, cetyl alcohol, and the like, and mixtures thereof. The molar ratio of at least one stabilizer to monomer is from about 0.004 to about 0.08, such as from about 0.005 to about 0.05. The molar ratio of at least one stabilizer to at least one compound to be stabilized is from about 0.1 to about 10, for example from about 0.5 to about 5.

  The dispersed latomer mixture is then subjected to high shear to produce a microemulsion. In embodiments, “microemulsion” refers to an aqueous dispersion of relatively stable hydrophobic microdroplets having a diameter of about 1.5 μm or less, such as about 1 μm or less. Shearing can be performed with various high shear mixing devices such as piston homogenizers, microfluidizers, polytrons, ultrasonic crushers, static mixers, and the like. In embodiments, for example, at a pressure of about 1,000 to about 30,000 psi (about 6.9 to about 207 MPa), such as about 5,000 to about 20,000 psi (about 34.5 to about 138 MPa), A piston homogenizer is used for 1 to about 60 minutes, for example about 5 to about 45 minutes to produce a microemulsion. Shear is defined as an impact force that reduces the size of a particle from microns to nanometers.

  Many additional components, such as at least one free radical initiator, may be added to the microemulsion at any point prior to the formation of the polymeric particles. In embodiments, at least one additional component can be added to the latomer mixture prior to shearing. In other embodiments, at least one additional component may be added to the microemulsion. All methods of adding additional ingredients are included herein.

  The microemulsion can further include at least one buffering agent such as alkali metal carbonate, alkaline earth carbonate, alkali metal bicarbonate, acetate, borate, and the like, and mixtures thereof. In embodiments, at least one buffer is added prior to formation of the microemulsion.

  The second heating step of the latomer mixture may be carried out at a polymerization temperature, for example from about 95 to about 145 ° C., more specifically for example from about 110 to about 125 ° C., for a reaction time, for example from about 2 to about 8 hours, more specifically for example It can be about 4 to about 6 hours. The heating conditions can be changed depending on, for example, the reaction scale and the desired result.

  The second heating step of the latomer mixture produces polymeric particles. These polymeric particles are mixed with at least one amine to aggregate / unify the polymeric particles. As used herein, at least one amine is water soluble and may have any number of functional groups, such as monoamines, diamines, and triamines, such as JEFFAMINE T-403 ( Trifunctional alkyl ether amine). At least one amine is reacted in the presence of a polymer containing at least one alkylene anhydride to form a polymer chain covalently bonded to each other. These chains can then be aggregated together to form larger chains and eventually particles.

  However, it is considered difficult to form an imide in an aqueous system in which the latomer mixture is stabilized in water. There are several precedents for imide formation in water. See Seijas, J. et al., “Microwave enhanced synthesis of bowl-shaped triimides with C3-symmetry,” Sixth International Electronic Conference on Synthetic Organic Chemistry, September 30, 2002.

  At least one amine is diamine, polyoxypropylenediamine, diethylenetriamine, 2-methylpentamethylenediamine, hexanediamine, hexamethylenediamine, N-isopropyl-N′-phenylphenylenediamine, N- (1,3-dimethylbutyl). -N'-phenylphenylenediamine, N, N'-di (2-octyl) -4-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -4-phenylenediamine, dihydroxytetraphenylbiphenylenediamine (DHTBD), and the like. The amount of at least one amine used depends on the amount of at least one alkylene anhydride. In embodiments, the content of at least one amine is from about 0.5 to about 10%, such as from about 1 to about 4% by weight, based on the amount of toner particles.

  In embodiments, the method has a high monomer to polymer conversion or degree of polymerization, such as greater than or equal to about 90% by weight, or about 95 to 100%, such as about 98 to about 100% (used in the method). (Conversion rate to all monomers). A composition comprising polymeric particles obtained after heating the microemulsion to a second polymerization temperature to produce polymeric particles is considered a latex or emulsion.

  In embodiments, the method can further comprise separating the polymeric particles (which are considered solids) from the liquid phase. Such separation can be performed by a general method such as filtration, precipitation, spray drying, and other similar known methods.

  The resulting polymer particles may have a weight average molecular weight (Mw) of, for example, about 3,000 to about 200,000, more specifically about 10,000 to about 150,000, for example. The polymeric particles may have a narrow polydispersity (PD), such as from about 1.1 to about 3, more specifically from about 1.1 to about 2, and even from about 1.05 to about 1.45, for example. it can. The volume average particle size of the polymeric particles is, for example, about 25 nm to about 50 μm, and more specifically, for example, about 100 nm to about 20 μm.

  If necessary, the polymer particles may be crosslinked in situ or as a separate post-polymerization processing using a known crosslinking agent or curing agent such as divinylbenzene. Known additives depending on the necessity, such as coloring agents, lubricants, release or transfer agents, antifoaming agents, antioxidants, etc., without affecting the method and adding performance to the resulting product. May be additionally used in the polymerization reaction.

  In embodiments, at least one wax can be added to the latomer mixture or microemulsion at any stage of the process. Examples of waxes include polypropylenes and polyethylenes commercially available from Allied Chemical and Petrolite Corporation, Michaelman Inc., and Daniels Products Company. ) Wax emulsions, EPOLENE N-15 (registered trademark) commercially available from Eastman Chemical Products, Inc., and VISCOL550, a low weight average molecular weight polypropylene manufactured by Sanyo Chemical Co., Ltd. -P (registered trademark), and similar materials may be mentioned, but are not limited thereto. Commercial polyethylenes used have a molecular weight (Mw) of about 700 to about 2,500, and commercially available polypropylenes have a molecular weight of about 4,000 to about 7,000. Examples of functionalized waxes such as amines and amides include, for example, AQUA SUPERSLIP 6550 (registered trademark), SUPERSLIP 6530 (registered trademark) manufactured by Micro Powder Inc .; fluorinated waxes For example, POLYFLUO 190 (registered trademark), POLYFLUO 200 (registered trademark), POLYFLUO 523XF (registered trademark), AQUA POLYFLUO 411 (registered trademark), AQUA POLYSILK 19 (registered trademark), and POLYSILK manufactured by Micro Powder Ink, Inc. 14 (registered trademark); a mixture of fluorinated waxes and amide waxes, such as MICROSPERSION 19 (registered trademark), also made by Micro Powder Ink; imides, esters, Quaternary amines, carboxylic acids, or acrylic polymer emulsions, eg, JONCRYL 74®, 89®, 130®, 537 (registered by SC Johnson Wax) And 538®; chlorinated polypropylenes and polyethylenes from Allied Chemical, Petrolite Corporations, and SC Johnson Wax. Suitable low molecular weight waxes are disclosed in US Pat. No. 4,659,641.

  The content of at least one wax is about 0.1 to about 15% by weight of the total monomer to be polymerized, such as about 2 to about 10% by weight. Alternatively, at least one wax may be added to the removed polymeric product of the process. The use of such components is preferred for certain toner applications.

  The toner composition can be produced in a number of known ways, and the resin or polymer particles obtained by the method herein can be obtained in a toner extruder such as ZSK53 from Werner Pfleiderer. The toner composition produced by heating and mixing can be produced by taking it out from the apparatus. After cooling, the toner composition is pulverized using, for example, a Sturtevant micronizer so that the volume median particle size of the toner particles is about 25 μm or less, for example, about 6 to about 14 μm. The diameter is obtained with a Coulter counter. Other methods include methods known in the art such as spray drying, melt dispersion, emulsion aggregation, and extrusion. Subsequently, the toner composition can be classified using, for example, a Donaldson B type classifier to remove the toner fine powder, that is, toner particles having a volume median particle size of about 4 μm or less. Alternatively, the toner composition may be pulverized using a fluidized bed pulverizer equipped with a classification wheel. In the embodiment, for example, at least one colorant is added to the microemulsion droplets before polymerization, and then the produced colored toner particles are taken out, so that the toner is directly manufactured without many particle size adjustment and separation steps. can do.

  Emulsion aggregation processes suitable for the production of the disclosed toner particles are described in many patents such as US Pat. No. 5,278,020, US Pat. No. 5,290,654, US Pat. No. 5,308,734, U.S. Patent 5,344,738, U.S. Patent 5,346,797, U.S. Patent 5,348,832, U.S. Patent 5,364,729, U.S. Patent 5,366,841, U.S. Patent No. 5,370,963, U.S. Patent No. 5,376,172, U.S. Patent No. 5,403,693, U.S. Patent No. 5,418,108, U.S. Patent No. 5,405,728, U.S. Patent No. 5,482,812, U.S. Patent No. 5,496,676, U.S. Patent No. 5,501,935, U.S. Patent No. 5,527,658, U.S. Patent No. 5,585,215, US Pat. No. 5,59 807, US Pat. No. 5,604,076, US Pat. No. 5,622,806, US Pat. No. 5,648,193, US Pat. No. 5,650,255, US Pat. No. 5,650. 256, US Pat. No. 5,658,704, US Pat. No. 5,660,965, US Pat. No. 5,723,253, US Pat. No. 5,744,520, US Pat. No. 5,763. 133, US Pat. No. 5,766,818, US Pat. No. 5,747,215, US Pat. No. 5,804,349, US Pat. No. 5,827,633, US Pat. No. 5,853 , 944, US Pat. No. 5,840,462, US Pat. No. 5,863,698, US Pat. No. 5,869,215, US Pat. No. 5,902,710, US Pat. No. 5,910 387, US Patent No. 5 916,725, U.S. Pat.No. 5,919,595, U.S. Pat.No. 5,922,501, U.S. Pat.No. 5,925,488, U.S. Pat.No. 5,945,245, U.S. Pat. No. 977,210, U.S. Patent No. 6,017,671, U.S. Patent No. 6,020,101, U.S. Patent No. 6,045,240, U.S. Patent No. 6,132,924, U.S. Patent No. 6, 143,457, and US Pat. No. 6,210,853. The ingredients and manufacturing methods of these patents can be used herein for their embodiments.

  Colorants include dyes and pigments such as US Pat. No. 4,788,123, US Pat. No. 4,828,956, US Pat. No. 4,894,308, US Pat. No. 4,948,686, It can be selected from those disclosed in US Pat. No. 4,963,455 and US Pat. No. 4,965,158. Examples of pigments include, but are not limited to black, cyan, magenta, yellow, green, orange, brown, amber, blue, red, purple, white, and silver. Examples of colorants include carbon black (eg, REGAL 3300®), Flexivese Pigment BFD1121, nigrosine dye, aniline blue, magnetites and colored magnetites (eg, Mobay magnetites, MO8029®). , MO8060 (registered trademark); Columbian magnetites, MAPICO BLACKS (registered trademark), and surface-treated magnetites; Pfizer magnetites, CB4799 (registered trademark), CB5300 (registered trademark), CB5600 (registered trademark) (Trademark), MCX6369 (registered trademark); Bayer magnetites, BAYFERROX 8600 (registered trademark), 8610 (registered trademark); Northern Pigments (Northern P) igments) magnetites, NP-604 (registered trademark), NP-608 (registered trademark); Magnox magnetites, TMB-100 (registered trademark), or TMB-104 (registered trademark)); phthalocyanines, 2,9-dimethyl substituted quinacridone, color index CI 60710, anthraquinone dye described as CI Dispersed Red 15, CI 26050 color index, diazo dye described as CI Solvent Red 19, copper = tetra (octadecylsulfonamide) phthalocyanine, The color index is CI 74160, X-copper phthalocyanine pigment described as CI Pigment Blue, the color index is CI 69810, Special Blue X-2137 Anthradanthrene Blue, diarylide yellow, 3,3-dichlorobenzidene acetoacetanilide, CI 12700 for color index, monoazo pigment described as CI Solvent Yellow 16, Foron Yellow SE / for color index GLN, nitrophenylaminesulfonamide described as CI Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilidephenylazo-4′-chloro-2,5-dimethoxyacetoacetanilide, Permanent Yellow FGL, Pigment Yellow 74, Sun B15: 3 cyan pigment dispersion manufactured by Sun Chemicals, Mag manufactured by Sun Chemicals nta Red 81: 3 pigment dispersion, San Chemicals, Ltd. of Yellow 180 pigment dispersion, a cyan component, etc., also mixtures thereof, are not limited to. Other commercially available pigment sources available as an aqueous pigment dispersion from Sun Chemicals or Ciba include Pigment Yellow 17, Pigment Yellow 14, Pigment Yellow 93, Pigment Yellow 74, Pigment Violet 23, Pigment 1 Volt. Pigment Green 7, Pigment Orange 36, Pigment Orange 21, Pigment Orange 16, Pigment Red 185, Pigment Red 122, Pigment Red 81: 3, Pigment Blue 15: Pigment Blue 15 Other pigments that can reproduce It is, but not limited to. Other suitable colorants include Cinquasia Magenta from DuPont; Miles, Bayer, Levanyl Black A-SF; Sun Chemical Carbon Black LHD9303, Sunsperse from Sun Chemicals. BHD6000, and Sunsperse Yellow YHD6001; all manufactured by Paul Uhlich, Normandy Magenta RD-2400, Permanent Yellow YE0305, Permanent Violet VT Ron ri Rli-Li R-Li R11 , Bri lllant Green Toner GR0991, and Ortho Orange OR2673; Sudrange Orange G, Tolidine Red, and E.M. from Aldrich. D. Toludine Red; made by Matheson, Coleman, Bell, Sudan III, Sudan II, and Sudan IV; made by Ugine Kuhlman, Canada; fort. Bon Red C manufactured by Dominion Color Co., all manufactured by BASF, Lumogen Yellow D0790, Suco-Gelb L1250, Suco-Yellow D1355, Palogenen Violet 5100, Palogen Orange 30Y, Paiogen Orange 30Y , Paligen Red 3871K, Palogen Red 3340, Pa iogen Yellow 1560, Paliogen Violet 5890, Paliogen Blue 6470, Lithol Scarlet 4440, Lithol Fast Scarlet L4300, Lithol Scarlet D3700, Lithol Fast Yellow 0991K, Paliotol Yellow 1840, Heliogen Green L8730, Heliogen Blue L6900, L7202, D6840, D7080, Neopen Blue , Sudan Blue OS, Sudan Orange 220 and Fanal Pink D4830; Cinquasia Magenta from DuPont; Novoperm Yell from Hoechst w FG1; Hostaper Pink E, and PV Fast Blue B2G01, all manufactured by American Hoechst; Irgalite Blue BCA, and Orect Pink RF, all manufactured by Ciba-Geigy. It is not limited to. Mixtures of colorants can also be used.

  Optionally, the colorant is present in a desired or effective amount in the toner composition, such as from about 1 to about 25%, such as from about 2 to about 15%, for example from about 2 to about 15% of the toner composition, such as the total weight of the toner composition. About 5 to about 12% by weight can be added. However, amounts beyond this range are possible.

  In embodiments, the styrene-maleic anhydride resin has at least one colorant covalently bound thereto, which is generally the reaction product of a monomeric colorant and styrene-maleic anhydride. Copolymers of styrene, butadiene, methoxy vinyl ether, ethylene, α-olefins, mixtures thereof, and the like and anhydrides all react with the monomeric colorant herein to produce a colored polymeric material. This is a preferred example of a polymeric material that can be formed.

  The toner composition can further contain a charge control additive, if desired. Such charge control additives include alkylpyridinium halides (such as cetylpyridinium chloride and those disclosed in US Pat. No. 4,298,672), sulfates and bisulfates (US Pat. No. 4,560). , 635, and distearyldimethylammonium methylsulfate, and U.S. Pat. No. 4,937,157, U.S. Pat. No. 4,560,635, and co-pending application 07 / 396,497 ( Disstely) and the like. 3,5-di-tert-butylsalicylic acid zinc compound (for example, Bontron E-84 manufactured by Orient Chemical Co., Ltd.), or US Pat. , 656,112, zinc compound disclosed in US Pat. No. 3,656,112, 3,5-di-tert-butylsalicylate aluminum Compound (for example, Bontron E-88 manufactured by Orient Chemical Co., Ltd.), or aluminum compound disclosed in US Pat. No. 4,845,003, US Pat. No. 3,944,493, US Pat. No. 4,007 No. 4,293, U.S. Pat. No. 4,079,014, U.S. Pat.No. 4,394,430, U.S. Pat.No. 4,464,452, U.S. Pat. No. 4,480,021, and U.S. Pat. And charge control additives disclosed in US Pat. No. 560,635, and mixtures thereof.

  The optional charge control additive content in the toner composition is from about 0.1 to about 10 weight percent, for example from about 1 to about 5 weight percent, based on the total weight of the toner composition. However, amounts beyond this range are possible.

  If necessary, an external surface additive such as a fluidity accelerator may be added to the toner composition. Such additives are generally present on the toner surface. Examples of external surface additives include metal oxides such as titanium oxide, tin oxide, mixtures thereof, colloidal silica such as AEROSIL®, zinc stearate, aluminum oxide, cerium oxide, and mixtures thereof. These metal salts and fatty acid metal salts are not limited to these. Some of the aforementioned additives are shown in US Pat. No. 3,590,000 and US Pat. No. 3,800,588. Further, the external surface additive may be a coated silica of US Pat. No. 6,004,714, US Pat. No. 6,190,815, and US Pat. No. 6,214,507. External surface additives can be added during the agglomeration process or mixed with the toner particles produced.

  Optional external surface additives can be added in any desired or effective amount, which amounts to about 0.1 to about 5% by weight, for example about 0.1, based on the total weight of the toner composition. To about 1% by weight. However, amounts beyond this range are possible.

  Although this specification has been described in detail with respect to specific embodiments thereof, these examples are illustrative and the specification is intended to limit the materials, conditions, or process parameters listed herein. It will be understood that it is not. All percentages and parts are by weight unless otherwise specified.

<Example 1>
Use of maleic anhydride in latex manufacturing processes

Maleic anhydride (16 g) was added to bulk polymerized styrene / butyl acrylate (200 ml, conversion about 20%, Mn = 1,900). The mixture was heated to about 50 ° C. until all maleic anhydride was dissolved. This was added to an aqueous solution (600 g of water and 16 g of sodium dodecylbenzenesulfonate (SDBS)) and stirred for 5 minutes. The resulting mixture was piston homogenized three times at 500 Bar (5 × 10 ⁷ Pa) and then transferred to a 1 liter BUCHI reactor. After pressurizing with argon, the pressure was reduced (5 times) to deoxygenate the latex microemulsion. Next, this was heated to 135 ° C. and left at this temperature for 1 hour, and then an ascorbic acid solution (8.5 ml having a concentration of 0.1 g / ml) was added at a rate of 0.035 ml / min using a pump. It was. After the reaction for 6 hours, the reaction mixture was allowed to cool to obtain a latex containing a resin having a content of about 200 μm, a solid content of 24.9%, Mn = 9,700, and Mw = 23,000.

<Example 2>
Aggregation of latex using diamines

To a stable free radical polymerization latex (707 g, solid content 23.48%), 660 ml of water and pigment (Cyan Blue BTD-FX-20, 47.8 g) were added. The mixture was stirred at room temperature, and diamine (Jeffamine D-400, 6.89 g in 100 ml of water) was added over 10 minutes. The resulting thick suspension was heated to 55 ° C. over 1 hour. Next, the pH of this suspension was raised to pH 7.3 using NaOH (concentrated). This was subsequently heated to 95 ° C. over 2 hours and kept at this temperature for 5 hours. The suspension was then allowed to cool, filtered, and washed 5 times with water until the filtrate conductivity was 15 microsiemens / cm ² or less. The obtained powder was resuspended in a small amount of water and freeze-dried to obtain 130 g of 13.4 μm particles.

<Example 3>
Use of maleic anhydride in bulk polymerization processes

  A stock solution of styrene (390 ml) and butyl acrylate (110 ml) was prepared, and TEMPO (3.12 g, 0.02 mol) and vazo64 initiator (2.0 g, 0.00125 mol) were added to 400 ml. . This was heated to 135 ° C. (bath temperature) in a nitrogen atmosphere, and then a maleic anhydride (9.8 g) solution dissolved in 100 ml of a styrene / butyl acrylate stock solution deoxygenated with nitrogen was added dropwise thereto. Poly (styrene / maleic anhydride-b-styrene / butyl acrylate) dissolved in styrene / butyl acrylate monomer after addition for 30 minutes and then stirring for an additional 5 minutes, then allowed to cool (Mn = 4,990, PD = 1.23) was obtained.

<Example 4>
Preparation of poly (styrene / maleic anhydride-b-styrene / butyl acrylate) latex

The polymer solution of Example 3 (300 ml), styrene (117 ml), butyl acrylate (33 ml) and TEMPO (0.6 g) were added to the SDBS solution (36 g in 1.2 liters of water) for 5 minutes. Stir. The mixture was then piston homogenized once at a pressure of about 500 Bar (5 × 10 ⁷ Pa) and then transferred to a 2 liter Buch reactor. This was heated to 135 ° C. (reactor temperature) and when the reactor reached this temperature, a total of 8.5 ml of ascorbic acid solution (2.4 g in 12 ml of water) was added at a drop rate of 0.0283 ml / min. After 6 hours at the reaction temperature, the reactor was allowed to cool to poly (styrene / maleic anhydride-b-styrene / butyl acrylate) (Mn = 39,168, PD = 1.64). 401.3 g of latex was removed.

<Example 5>
Aggregation / unification of latex using diamine as coagulant

  50 ml of water was added to the latex (50 ml) prepared in Example 4 and the pH was adjusted to about 1.78 with stirring at room temperature. To this, 2.89 g of Jeffamine D400 solution (20 vol% aqueous solution) was added dropwise at 23-25 ° C., and then slowly heated to 60 ° C. over about 1 hour. The particle size grew from about 200 nm to 6.8 μm. After adjusting the pH of the solution to 9.04 using dilute NaOH solution, the solution was slowly heated to 95 ° C. over about 1.5 hours, and kept at this temperature for 1.5 hours to obtain a particle size of 6.68 μm (Mn = 39,168) of white coalesced particles.

Claims (2)

And at least one free-radically polymerizable monomer, a first heating step of heating at least one aliphatic carboxylic acid anhydride, an the including mixed compounds,
After the first heating step, using high shear to disperse the mixture in an immiscible liquid to produce a miniemulsion;
A second heating step to produce a polymer particle by heating the pre-Symbol mixed compound,
To aggregate the polymer particles, a step of coupling at least one amine to the polymer particles,
Toner production method, including.   2. The toner manufacturing method according to claim 1, wherein the temperature of the first heating step is about 50 to about 145 ° C. 3.